The Influence of Cooling Rate on the Specific Volume of Isotactic Poly(propylene) at Elevated Pressures

Summary: We used a custom designed dilatometer to measure quantitatively the time evolution of the specific volume of (semi‐crystalline) polymers for an unusual combined wide range of cooling rates and elevated pressures, covering processing conditions. For an isotactic poly(propylene), applying the Schneider rate equations for quiescent crystallization, experimental results are compared to numerical predictions. Average cooling rates imposed during crystallization of the material vary from 0.1 to 35 °C · s^?1 while pressures range from 20 to 60 MPa. The results show the well‐known profound influence of pressure and cooling rate on the specific volume. An increasing cooling rate shifts the crystallization temperature T_c towards lower temperatures, increases the final specific volume, and the transition due to crystallization is more gradual and widespread. For the highest cooling rate applied, the shift in T_c is as much as 30 °C, while the final specific volume increases up to 1.4%. Increasing pressure has an opposite effect on the shift in T_c, while the final specific volume, after pressure release, also increases. Finally, a comparison of numerical predictions with experimental data shows that the crystallization temperature T_c is consistently predicted too low, and that the predictions at high cooling rate are sensitive to (small) variations in model parameters.

Influence of cooling rate on the specific volume of iPP.     

Counting and particle transmission efficiency of the aerodynamic particle sizer

The aerodynamic particle sizer (APS) measures the size distributions of particles with aerodynamic diameter between 0.5 and in real time. To provide accurate size distributions, the APS must measure both particle size and concentration correctly. The objective of this study was to characterize the counting efficiency of the APS as a function of particle size (0.8–), particle type (liquid or solid), and APS model number (3310 vs. 3321). For solid particles, counting efficiencies ranged between 85% and 99%. For liquid droplets, counting efficiencies progressively declined from 75% at 0.8-μm drops to 25% for 10-μm drops. Fluorometric wash tests indicated that transmission losses occur when larger droplets impact on the instrument's inner nozzle. However, transmission losses did not account entirely for the reduced droplet counting efficiencies, indicating that additional losses may have occurred downstream of the inner nozzle. Between instrument comparisons revealed that although multiple APSs report similar number concentrations, small deviations in particle sizing can produce substantial errors when number concentrations are converted to mass concentrations.     

NMR microscopy of single neurons at 500 MHZ

Previous NMR microimaging studies at 360 MHz have demonstrated a clear differentiation between the nucleus and cytoplasm in isolated single neurons. In particular, theT ₂ of the cell nucleus is 2.5 times larger than that of the cytoplasm. In order to determine the magnitude of possibleT ₂ ^* influences on these observations, images of single cells have been obtained at 500 MHz using spin-echo and line-narrowing sequences. Comparison of the images acquired by the two sequences, and of the spin-echo images at 360 and 500 MHz, imply that anyT ₂ ^* contributions are relatively small. Consequently, the measuredT ₂ differences in spin-echo imaging represent a true difference in theT ₂ relaxation in the two cellular compartments.     

Prediction of pyrolysis of pistachio shells based on its components hemicellulose, cellulose and lignin

The objective of this contribution is to describe thermal degradation of pistachio shells by a detailed reaction mechanism. Pistachio shells are assumed to be composed of hemicellulose, cellulose and lignin of which degradation is described by relevant kinetics based on experimental data. The mechanism yields a detailed composition of product gases, and therefore, is well-suited to predict evolution of both thermal decomposition and products. Thermal degradation is described by a system of coupled differential conservation equations for mass, momentum, species, and energy for a pistachio shell particle. The relevant conservation equations are discretised by the Finite Volume Method (FVM) and solved within the conversion module of the Discrete Particle Method (DPM). A comparison between experimental data and predicted results yielded good agreement.     

Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

Decomposition kinetics and recycle of hydrogen–tetrahydrofuran (H₂–THF) clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1 to 8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm. The decomposition was modeled as a two‐step process consisting of H₂ diffusion in the hydrate phase and desorption from the hydrate cage. The adsorption process occurred at roughly two to three times faster than the desorption process, whereas the diffusion process during formation was slightly higher (ca. 20%) than that during decomposition. Successive formation and decomposition cycles showed that occupancy seemed to decrease only slightly with cycling and that there were no large changes in hydrate structure due to cycling. Results provide evidence that the formation and decomposition of H₂ clathrate hydrates occur reversibly and that H₂ clathrate hydrates can be recycled with pressure. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Exploring the potential of recovering 1‐butanol from aqueous solutions by liquid demixing upon addition of carbohydrates or salts

BACKGROUND: Fermentative production of 1‐butanol yields dilute aqueous solutions. Recovery of the butanol from these solutions is most commonly performed by energy‐intensive distillation. This work investigated the liquid‐liquid (L‐L) phase behavior of mixtures of butanol and water to explore the potential of using L‐L phase separation as a recovery possibility for 1‐butanol. The phase behavior is preferably influenced by compounds already present in the fermentation, such as carbohydrates and salts. RESULTS: The L‐L phase equilibria of butanol and water were determined in the presence of glucose, fructose, sucrose, NaCl, LiCl and CaCl₂. The aqueous and organic phase split is more pronounced in the presence of salts than in the presence of carbohydrates. Demixing is achieved with about 0.3 kg salt kg^?1 aqueous phase containing 40 g of butanol. CONCLUSION: Operation of L‐L based recovery using salts or carbohydrates requires extreme concentrations of those compounds. For feed material containing 40 g kg^?1 butanol, the tested carbohydrates do not influence the phase equilibria sufficiently to allow butanol separation. Fermentative butanol concentrations up to 70 g kg^?1 are required to create an effective L‐L phase split. The remaining residual aqueous carbohydrate solution might be used as feed for a following fermentation. Copyright © 2011 Society of Chemical Industry     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

An improved accelerated weathering protocol to anticipate Florida exposure behavior of coatings

A new accelerated weathering protocol has been developed which closely replicates the performance of automotive and aerospace coating systems exposed in South Florida. IR spectroscopy was used to verify that the chemical composition changes that occurred during accelerated weathering in devices with a glass filter that produced a high fidelity reproduction of sunlight’s UV spectrum matched those that occurred during natural weathering. Gravimetric water absorption measurements were used to tune the volume of water absorption during accelerated weathering to match that which occurred during natural weathering in South Florida. The frequency of water exposure was then scaled to the appropriate UV dose. A variety of coating systems were used to verify the correlation between the physical failures observed in the accelerated weathering protocol and natural weathering in South Florida. The new accelerated weathering protocol correctly reproduced gloss loss, delamination, cracking, blistering, and good performance in a variety of diverse coating systems. For automotive basecoat/clearcoat paint systems, the new weathering protocol shows significant acceleration over both Florida and previous accelerated weathering tests. For monocoat aerospace systems, the new weathering protocol showed less acceleration than for automotive coatings, but was still an improvement over previous accelerated tests and was faster than Florida exposure.